Oxidation Of Sulfides Research Articles

Cation Vacancies Enable Anion Redox in Li Cathodes.

Conventional Li-ion battery intercalation cathodes leverage charge compensation that is formally associated with redox on the transition metal. Employing the anions in the charge compensation mechanism, so-called anion redox, can yield higher capacities beyond the traditional limitations of intercalation chemistry. Here, we aim to understand the structural considerations that enable anion oxidation and focus on processes that result in structural changes, such as the formation of persulfide bonds. Using a Li-rich metal sulfide as a model system, we present both first-principles simulations and experimental data that show that cation vacancies are required for anion oxidation. First-principles simulations show that the oxidation of sulfide to persulfide only occurs when a neighboring vacancy is present. To experimentally probe the role of vacancies in anion redox processes, we introduce vacancies into the Li2TiS3 phase while maintaining a high valency of Ti. When the cation sublattice is fully occupied and no vacancies can be formed through transition metal oxidation, the material is electrochemically inert. Upon introduction of vacancies, the material can support high degrees of anion redox, even in the absence of transition metal oxidation. The model system offers fundamental insights to deepen our understanding of structure-property relationships that govern reversible anion redox in sulfides and demonstrates that cation vacancies are required for anion oxidation, in which persulfides are formed.

Synthesis, characterization, and a comparative study on the catalytic activity of the functionalized magnetic nanoparticles for the green oxidation of sulfides

AbstractIn the following research, meso‐tetrakis(4‐carboxyphenyl)porphyrinatomanganese (III) acetate (MnTCPP(OAc)) was immobilized onto the surface of two functionalized magnetic nanoparticles (MNPs) with different linker length via amide bond (Fe3O4@SiO2‐NH2‐MnTCPP(OAc) (A1) and Fe3O4@SiO2‐NHCO‐NH2‐MnTCPP(OAc) (A2)). The prepared catalysts were characterized by standard methods such as: atomic absorption spectroscopy (AAS), Ultra violet‐visible (UV‐Vis), Fourier‐transform infrared (FT‐IR), vibrating sample magnetometry (VSM), field emission scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM) techniques and also the effect of the length of the linker on the catalytic activity of supported magnetic nanohybrids was investigated. The prepared magnetic nano‐catalysts with different linker lengths were participated in a comparative study of the clean oxidation of sulfides with urea hydrogen peroxide (UHP) in ethanol. The higher catalytic activity, selectivity and also reusability were achieved in the presence of the catalyst with longer linker length (A2) at ambient temperature. Moreover, the turnover number (TON) of catalytic reactions using A2 as catalyst was highly enough to consider the catalyst as an efficient material to oxidize various sulfides. Both A1 and A2 catalysts simply have accomplished 5 runs of recycling without significant decrease in the catalytic activity.

Synergistic catalytic effect of titanium and iron incorporated to spherical MCM-41 in selective catalytic oxidation of diphenyl sulphide with H2O2

Spherical mesoporous silicas of MCM-41 type modified with titanium, iron or both these metals were prepared by co-condensation method and tested in the role of catalysts for selective oxidation of diphenyl sulphide with H2O2 to diphenyl sulphoxide and diphenyl sulphone. The monometallic catalysts containing titanium or iron were found to be active catalysts of diphenyl sulphide mainly to diphenyl sulphoxide. A very significant increase in catalytic activity was observed for the bimetallic samples, containing both titanium and iron. Moreover, in the case of bimetallic catalysts with higher titanium loading, diphenyl sulphone is a dominating reaction product. The increased activity of the bimetallic catalysts has been related to the synergistic operation of titanium and iron in conversion of hydrogen peroxide into reactive species, which in the next step oxidise diphenyl sulphoxide.

Integrating Polyoxometalates and Silver Clusters into Atomically Precise Molecular Heterojunction.

The Ag cluster-POM assemblies have been shown to possess interesting and potentially useful properties. However, there is no precedent example of atomically precise Ag cluster-POM assemblies showing heterojunction effects in photocatalysis. Herein, the synthesis and total structure determination of the periodically distributed molecular heterojunction [Ag12(SCy)6(CH3CN)12(PW12O40)]n (Ag12-PW12) are reported. The assembly of Ag/W clusters into 3D network can endow the resulting binary structure with an aesthetic topology and unique physicochemical properties. More remarkably, the incorporation of Ag12 cluster with PW12 can efficiently facilitate the separation of photogenerated electrons and holes, thus significantly promoting the catalytic efficiency in selective oxidation of sulfides. The Ag12-PW12 heterojunction can be recovered and reused five times with no drastic change in the catalytic performance. This research is expected to assist in the rational design of cluster-based heterojunction catalysts. The increase of catalytic activity of the Ag12-PW12 assembly in comparison with the unassembled Ag12 and PW12 clusters is attributed to the synergistic effect of Ag12 and PW12 clusters, offering the splendid opportunity for deciphering structure-reactivity relationship of heterostructure-coupled photosystem.

Phytomelatonin: From Intracellular Signaling to Global Horticulture Market.

Melatonin (N-acetyl-5-methoxytryptamine), a well-known mammalian hormone, has been having a great relevance in the Plant World in recent years. Many of its physiological actions in plants are leading to possible features of agronomic interest, especially those related to improvements in tolerance to stressors and in the postharvest life of fruits and vegetables. Thus, through the exogenous application of melatonin or by modifying the endogenous biosynthesis of phytomelatonin, some change can be made in the functional levels of melatonin in tissues and their responses. Also, acting in the respective phytomelatonin biosynthesis enzymes, regulating the expression of tryptophan decarboxylase (TDC), tryptamine 5-hydroxylase (T5H), serotonin N-acetyltransferase (SNAT), N-acetylserotonin O-methyltransferase (ASMT), and caffeic acid O-methyltransferase (COMT), and recently the possible action of deacetylases on some intermediates offers promising opportunities for improving fruits and vegetables in postharvest and its marketability. Other regulators/effectors such as different transcription factors, protein kinases, phosphatases, miRNAs, protein-protein interactions, and some gasotransmitters such as nitric oxide or hydrogen sulfide were also considered in an exhaustive vision. Other interesting aspects such as the role of phytomelatonin in autophagic responses, the posttranslational reprogramming by protein-phosphorylation, ubiquitylation, SUMOylation, PARylation, persulfidation, and nitrosylation described in the phytomelatonin-mediated responses were also discussed, including the relationship of phytomelatonin and several plant hormones, for chilling injury and fungal decay alleviating. The current data about the phytomelatonin receptor in plants (CAND2/PMTR1), the effect of UV-B light and cold storage on the postharvest damage are presented and discussed. All this on the focus of a possible new action in the preservation of the quality of fruits and vegetables.

Exogenous hydrogen sulfide mitigates potassium deficiency in Brassica napus plants by modulating growth and photosynthetic activity and regulating hydrogen sulfide and nitric oxide biosynthesis

Exogenous hydrogen sulfide mitigates potassium deficiency in Brassica napus plants by modulating growth and photosynthetic activity and regulating hydrogen sulfide and nitric oxide biosynthesis

Single Amino Acids as Sole Nitrogen Source for the Production of Lipids and Coenzyme Q by Thraustochytrium sp. RT2316-16.

This work analyzes the production of total lipids and the content of CoQ9 and CoQ10 in the biomass of Thraustochytrium sp. RT2316-16 grown in media containing a single amino acid at a concentration of 1 g L-1 as the sole nitrogen source; glucose (5 g L-1) was used as the carbon source. Biomass concentration and the content of total lipids and CoQ were determined as a function of the incubation time; ten amino acids were evaluated. The final concentration of the total biomass was found to be between 2.2 ± 0.1 (aspartate) and 3.9 ± 0.1 g L-1 (glutamate). The biomass grown in media containing glutamate, serine or phenylalanine reached a content of total lipids higher than 20% of the cell dry weight (DW) after 72, 60 and 72 h of incubation, respectively. The highest contents of CoQ9 (39.0 ± 0.7 µg g-1 DW) and CoQ10 (167.4 ± 3.4 mg g-1 DW) in the biomass of the thraustochytrid were obtained when glutamate and cysteine were used as the nitrogen source, respectively. Fatty acid oxidation, which decreased the total lipid content during the first 12 h of incubation, and the oxidation of hydrogen sulfide when cysteine was the nitrogen source, might be related to the content of CoQ10 in the biomass of the thraustochytrid.

Pan-Arctic methanesulfonic acid aerosol: source regions, atmospheric drivers, and future projections

Natural aerosols are an important, yet understudied, part of the Arctic climate system. Natural marine biogenic aerosol components (e.g., methanesulfonic acid, MSA) are becoming increasingly important due to changing environmental conditions. In this study, we combine in situ aerosol observations with atmospheric transport modeling and meteorological reanalysis data in a data-driven framework with the aim to (1) identify the seasonal cycles and source regions of MSA, (2) elucidate the relationships between MSA and atmospheric variables, and (3) project the response of MSA based on trends extrapolated from reanalysis variables and determine which variables are contributing to these projected changes. We have identified the main source areas of MSA to be the Atlantic and Pacific sectors of the Arctic. Using gradient-boosted trees, we were able to explain 84% of the variance and find that the most important variables for MSA are indirectly related to either the gas- or aqueous-phase oxidation of dimethyl sulfide (DMS): shortwave and longwave downwelling radiation, temperature, and low cloud cover. We project MSA to undergo a seasonal shift, with non-monotonic decreases in April/May and increases in June-September, over the next 50 years. Different variables in different months are driving these changes, highlighting the complexity of influences on this natural aerosol component. Although the response of MSA due to changing oceanic variables (sea surface temperature, DMS emissions, and sea ice) and precipitation remains to be seen, here we are able to show that MSA will likely undergo a seasonal shift solely due to changes in atmospheric variables.

Remediation of Sulfides in Produced Waters of the Oil and Gas Industry Using Hydrogen Peroxide

Produced waters are often treated in open lagoons where hydrogen sulfide (H2S) can off gas, posing a risk to human health and the environment. The aim of this study was to optimize a treatment process using hydrogen peroxide (H2O2) to oxidize H2S while minimizing off gassing. Samples of produced water from West Texas and laboratory-prepared waters utilizing sodium sulfide (Na2S) or biogenic polysulfides were oxidized with H2O2 alone or in combination with copper or iron catalysts, sodium hydroxide (NaOH), or a commercial sulfide oxidizer, HydroPower Green™. Sulfur speciation was measured using Hach test kits for sulfide/sulfate/sulfite and Dräger tubes for headspace H2S. HydroPower Green™ (HPG) helped to reduce H2S in the headspace of water samples; some of this was pH related as NaOH also worked, but not as well as HPG. The dose of peroxide necessary to oxidize sulfides to sulfate is a function of the oxidation-reduction potential (Eh) of the water and total sulfide concentration as well as pH; approximately a 1–4:1 ratio of peroxide to sulfide concentration was needed to oxidize sulfidic waters of pH 7–10 with half-lives under 30 min. Both copper and iron catalysts reduce H2O2 demand and the half-life of H2S. Peracetic acid (PAA) and copper (II) sulfate pentahydrate (CuSO4, 5H2O) were explored as biocides for controlling sulfate-reducing bacteria (SRBs) that produce H2S. An AquaSnap (Hygenia) test kit was employed to monitor relative microbial activity in a wetland porewater containing H2S. Microbial regrowth occurred after a few days using the highest dose of PAA; these results showed that PAA was being used by bacteria as a carbon source even after the initial substantial reduction in the microbial activity. CuSO4, 5H2O at a dose of 1 ppm prevented microbial regrowth. The recommended treatment process from this research is determined by jar testing with H2O2, a base for pH control, a biocide, and possibly a metal catalyst or other co-oxidants in order to achieve oxidation of sulfides without H2S release or the precipitation of metal carbonates or oxides.

Seawater barium and sulfide removal improved marine habitability for the Cambrian Explosion of early animals.

An increase in atmospheric pO2 has been proposed as a trigger for the Cambrian Explosion at ∼539-514Ma but the mechanistic linkage remains unclear. To gain insights into marine habitability for the Cambrian Explosion, we analysed excess Ba contents (Baexcess) and isotope compositions (δ138Baexcess) of ∼521-Myr-old metalliferous black shales in South China. The δ138Baexcess values vary within a large range and show a negative logarithmic correlation with Baexcess, suggesting a major (>99%) drawdown of oceanic Ba inventory via barite precipitation. Spatial variations in Baexcess and δ138Baexcess indicate that Ba removal was driven by sulfate availability that was ultimately derived from the upwelling of deep seawaters. Global oceanic oxygenation across the Ediacaran-Cambrian transition may have increased the sulfate reservoir via oxidation of sulfide and concurrently decreased the Ba reservoir by barite precipitation. The removal of both H2S and Ba that are deleterious to animals could have improved marine habitability for early animals.

Constructing An Oxyhalide Interface for 4.8 V‐Tolerant High‐Nickel Cathodes in All‐Solid‐State Lithium‐Ion Batteries

AbstractAll‐solid‐state lithium batteries (ASSBs) have received increasing attentions as one promising candidate for the next‐generation energy storage devices. Among various solid electrolytes, sulfide‐based ASSBs combined with layered oxide cathodes have emerged due to the high energy density and safety performance, even at high‐voltage conditions. However, the interface compatibility issues remain to be solved at the interface between the oxide cathode and sulfide electrolyte. To circumvent this issue, we propose a simple but effective approach to magic the adverse surface alkali into a uniform oxyhalide coating on LiNi0.8Co0.1Mn0.1O2 (NCM811) via a controllable gas‐solid reaction. Due to the enhancement of the close contact at interface, the ASSBs exhibit improved kinetic performance across a broad temperature range, especially at the freezing point. Besides, owing to the high‐voltage tolerance of the protective layer, ASSBs demonstrate excellent cyclic stability under high cutoff voltages (500 cycles~94.0 % at 4.5 V, 200 cycles~80.4 % at 4.8 V). This work provides insights into using a high voltage stable oxyhalide coating strategy to enhance the development of high energy density ASSBs.

Constructing An Oxyhalide Interface for 4.8 V-Tolerant High-Nickel Cathodes in All-Solid-State Lithium-Ion Batteries.

All-solid-state lithium batteries (ASSBs) have received increasing attentions as one promising candidate for the next-generation energy storage devices. Among various solid electrolytes, sulfide-based ASSBs combined with layered oxide cathodes have emerged due to the high energy density and safety performance, even at high-voltage conditions. However, the interface compatibility issues remain to be solved at the interface between the oxide cathode and sulfide electrolyte. To circumvent this issue, we propose a simple but effective approach to magic the adverse surface alkali into a uniform oxyhalide coating on LiNi0.8Co0.1Mn0.1O2 (NCM811) via a controllable gas-solid reaction. Due to the enhancement of the close contact at interface, the ASSBs exhibit improved kinetic performance across a broad temperature range, especially at the freezing point. Besides, owing to the high-voltage tolerance of the protective layer, ASSBs demonstrate excellent cyclic stability under high cutoff voltages (500 cycles~94.0 % at 4.5 V, 200 cycles~80.4 % at 4.8 V). This work provides insights into using a high voltage stable oxyhalide coating strategy to enhance the development of high energy density ASSBs.

Iodonium Salt‐Mediated Oxidation of Sulfides to Sulfoxides by DMSO

Iodonium Salt‐Mediated Oxidation of Sulfides to Sulfoxides by DMSO

Lithium cation-doped tungsten oxide as a bidirectional nanocatalyst for lithium-sulfur batteries with high areal capacity

Lithium-sulfur (Li-S) batteries are promising for high energy-storage applications but suffer from sluggish conversion reaction kinetics and substantial lithium sulfide (Li2S) oxidation barrier, especially under high sulfur loadings. Here, we report a Li cation-doped tungsten oxide (LixWOx) electrocatalyst that efficiently accelerates the S↔Li2S interconversion kinetics. The incorporation of Li dopants into WOx cationic vacancies enables bidirectional electrocatalytic activity for both polysulfide reduction and Li2S oxidation, along with enhanced Li+ diffusion. In conjunction with theoretical calculations, it is discovered that the improved electrocatalytic activity originates from the Li dopant-induced geometric and electronic structural optimization of the LixWOx, which promotes the anchoring of sulfur species at favourable adsorption sites while facilitating the charge transfer kinetics. Consequently, Li-S cells with the LixWOx bidirectional electrocatalyst show stable cycling performance and high sulfur utilization under high sulfur loadings. Our approach provides insights into cation engineering as an effective electrocatalyst design strategy for advancing high-performance Li-S batteries.

Diethyl Sulfide Oxidation with Sodium Peroxoborate in Water–Acetonitrile System. Kinetics and Mechanism

In aqueous solutions of acetonitrile (1 vol%), the rate of oxidation of diethyl sulfide with sodium peroxoborate, Na2[B2(O2)2(OH)4]∙6H2O, in the pH range of 8.5–11 is significantly higher than the oxidation rate in water and exceeds the rate of reaction of Et2S with hydrogen peroxide in the H2O–MeCN system. The reaction order with respect to the substrate, which is close to zero, suggests that the limiting stage of the process is the reaction of peroxoborate anions with MeCN, leading to the formation of active boron peroxyimidates, which then react in a rapid stage with Et2S.

A heterogeneous catalyst for oxidation of sulfides using a Mn(II) unsymmetrical Schiff base complex immobilized on MCM-41

An unsymmetrical Mn(II) Schiff base complex was attached to MCM-41. The synthesized catalyst was characterized by powder X-ray diffraction (XRD), nitrogen adsorption/desorption isotherms, inductivity coupled plasma (ICP), Fourier Transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The immobilized Schiff base complex was an efficient catalyst for oxidation of sulfides with hydrogen peroxide. In addition, this green oxidation system was used to oxidize various sulfides and the results showed that sulfoxides were the major products. Finally, the reuse of the catalyst was also investigated

Multi-method characterization of groundwater nitrate and sulfate contamination by karst mines in southwest China

Groundwater contamination by nitrate and sulfate in mining areas is a significant challenge. Consequently, the inputs sources of these contaminants and their evolution have received considerable attention, with the knowledge gained critical for improved management of water quality. This study integrated data on multiple stable isotopes and water chemistry data and a Bayesian isotope mixing model to investigate the relative contributions of inputs sources of sulfate and nitrate sources to bodies of water in a karst mining area in southwest China. The outcomes indicated that hydrochemical component in the water bodies of the study area is mainly derived from the dissolution of silicate rocks, carbonate rocks and sulfate minerals as well as the oxidation of sulfides. The human and agricultural wastewater, soil nitrogen, and fertilizers were the predominant inputs sources of nitrate to the mine water environment; the predominant inputs sources of sulfide were mineral oxidation, evaporite dissolution, atmospheric deposition, and sewage. Groundwater is mainly recharged from atmospheric precipitation, and surface water is closely hydraulically connected to groundwater. Nitrogen and oxygen isotope composition and water chemistry indicative of nitrification dominate the nitrogen cycle in the study area. The oxidation of pyrite and bacterial sulfate reduction (SRB) had no significant impact on the stable isotopes of groundwater. The results of this study demonstrate the inputs of different sources to nitrate and sulfate in karst mines and associated transformation processes. The results of this study can assist in the conservation of groundwater quality in mining areas and can act as a reference for future related studies.

Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants

Visible-light-driven oxidation of sulfides has attracted the profound attention to synthesize sulfoxides and purify mustard gas simulant. In this work, a series of visible-light-responsive polyoxometalate-based porous cationic polymers, i.e. SiW12-PCP 1, PW12-PCP 2, SiW11-PCP 3, SiW10-PCP 4, SiW9-PCP 5 (PCP = porphyrin-based porous cationic polymer), were synthesized by ion exchange process. These POM-PCPs exhibit excellent ability of trapping visible light due to their built-in porphyrin units, which can rapidly oxidize sulfides and degrade 2-chloroethyl ethyl sulfide (CEES) in the presence of a 10 W white LED light and O2. Benefiting from the synergistic effect between [SiW12] and PCP, hybrid 1 has the highest photocatalytic efficiency, attaining 99 % conversion of sulfides within 16 min and 99 % CEES purification in 8 min, much higher than PCP precursor. The reaction mechanism reveals that both O2•− and 1O2 are involved in the photocatalytic process. What's more, hybrid 1 has remarkable applicability to numerous sulfides and robust six-round recycling with no reduction in catalytic efficiency.

Diversity, Methane Oxidation Activity, and Metabolic Potential of Microbial Communities in Terrestrial Mud Volcanos of the Taman Peninsula.

Microbial communities of terrestrial mud volcanoes are involved in aerobic and anaerobic methane oxidation, but the biological mechanisms of these processes are still understudied. We have investigated the taxonomic composition, rates of methane oxidation, and metabolic potential of microbial communities in five mud volcanoes of the Taman Peninsula, Russia. Methane oxidation rates measured by the radiotracer technique varied from 2.0 to 460 nmol CH4 cm-3 day-1 in different mud samples. This is the first measurement of high activity of microbial methane oxidation in terrestrial mud volcanos. 16S rRNA gene amplicon sequencing has shown that Bacteria accounted for 65-99% of prokaryotic diversity in all samples. The most abundant phyla were Pseudomonadota, Desulfobacterota, and Halobacterota. A total of 32 prokaryotic genera, which include methanotrophs, sulfur or iron reducers, and facultative anaerobes with broad metabolic capabilities, were detected in relative abundance >5%. The most highly represented genus of aerobic methanotrophs was Methyloprofundus reaching 36%. The most numerous group of anaerobic methanotrophs was ANME-2a-b (Ca. Methanocomedenaceae), identified in 60% of the samples and attaining relative abundance of 54%. The analysis of the metagenome-assembled genomes of a community with high methane oxidation rate indicates the importance of CO2 fixation, Fe(III) and nitrate reduction, and sulfide oxidation. This study expands current knowledge on the occurrence, distribution, and activity of microorganisms associated with methane cycle in terrestrial mud volcanoes.

Oxygen-assisted catalytic oxidation of hydrogen sulfide in crude oil

Oxygen-assisted catalytic oxidation of hydrogen sulfide in crude oil